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5in swp0001

Chapter 3

UNIFAC and Its Related Calculations

Example 3.1 For the binary system diethylamine (1).n-heptane(2) at 308.15 K,

…nd 1 and 2 when x1 = 0:4. The chemical formulas are given as CH3 -CH2 NH-
CH2 -CH3 (1) and CH3 -(CH2 )5 -CH3 (2). The …gure below illustrates the chemical
structure for diethylamine and n-heptane)

H H
H H
H H H H H H H H H

H H

H H H H H H H H H
n-heptane N
H H

H
diethylamine

Fig. 3.1 Chemical structure for diethylamine (1) and n-heptane (2).

The following table shows the subgroups and their identi…cation numbers k,
values of parameters Rk and Qk , and the number of each subgroup in each molecule:
Obtain the volume contribution for each molecule as:
X (i)
ri = k Rk ;
k
r1 = (2)(0:9011) + (1)(0:6744) + (1)(1:2070) = 3:6836
r2 = (2)(0:9011) + (5)(0:6744) = 5:1742

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diethylamine (1) n-heptane (2)

(1) (2)
Subgroup k Rk Qk k k
CH3 1 0.9011 0.848 2 2
CH2 2 0.6744 0.540 1 5
CH2 NH 33 1.2070 0.936 1 0

In like manner for the surface fractions

X (i)
qi = k Qk ;
k
q1 = (2)(0:848) + (1)(0:540) + (1)(0:936) = 3:1726
q2 = (2)(0:848) + (5)(0:540) = 4:3960

The ri and qi values are molecular properties, independent of composition. Sub-

stitute the known values to obtain the eki which are the surface fractions for each
subgroup in each molecule. The size of this matrix is the number of subgroups times
the number of components i.e., for this example it is 3 2.

(i)
k Qk
ek;i =
qi
(1)
1 Q1 2(0:848)
e1;1 = = = 0:5347
q1 3:1726
(2)
1 Q1 2(0:848)
e1;2 = = = 0:3858
q2 4:3960
(1)
2 Q2 1(0:540)
e2;1 = = = 0:1702
q1 3:1726
(2)
2 Q2 5(0:540)
e2;2 = = = 0:6142
q2 4:3960
(1)
3 Q3 1(0:936)
e33;1 = = = 0:2951
q1 3:1726
(2)
3 Q3 0(0:936)
e33;2 = = =0
q2 4:396

ek;i
k i=1 i=2
1 0.5347 0.3858
2 0.1702 0.6142
33 0.2951 0.0000
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Determine the overall surface area fraction for each subgroup in the mixture
which is a vector of size k. The fraction is de…ned as

P
xi qi ek;i
i
k = P
xj qj
j
P
xi qi e1;i
i 0:4(3:1762)(0:5347) + 0:6(4:3960)(0:3858)
1 = P = = 0:4342
xj qj 0:4(3:1762) + 0:6(4:3960)
j
P
xi qi e2;i
i 0:4(3:1762)(0:1702) + 0:6(4:3960)(0:6142)
2 = P = = 0:4700
xj qj 0:4(3:1762) + 0:6(4:3960)
j
P
xi qi e33;i
i 0:4(3:1762)(0:2951) + 0:6(4:3960)(0:0000)
33 = P = = 0:0958
xj qj 0:4(3:1762) + 0:6(4:3960)
j

Obtain the interaction parameters matrix for the subgroups from the table. This
is a square matrix whose elements are determined by the number of subgroups i.e.,
for this example it is 3 3. Notice that ai;i = 0:0

1 2 33
1 a1;1 = 0:0 a1;2 = 0:0 a1;33 = 255:7
am;k =
2 a2;1 = 0:0 a2;2 = 0:0 a2;33 = 255:7
33 a33;1 = 65:33 a33;2 = 65:33 a33;33 = 0:0

From this matrix, at the given temperature T = 308:15 K, determine the m;k from

h a i
m;k
m;k = exp
T
1;1 = 1 1;2 =1 1;33 = 0:4361
m;k = 2;1 = 1 2;2 = 1 2;33 = 0:4361
33;1 = 0:8090 33;2 = 0:8090 33;33 = 1
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Determine the ik . The size of this matrix is number of components times the
number of subgroups i.e., for this example it is 2 3.

X
ik = emi m;k
m
X
1;1 = em1 m;1 = 0:5347(1) + 0:1702(1) + 0:2951(0:8090) = 0:9436
m
X
1;2 = em1 m;2 = 0:5347(1) + 0:1702(1) + 0:2951(0:8090) = 0:9436
m
X
1;33 = em1 m;33 = 0:5347(0:4361) + 0:1702(0:4361) + 0:2951(1) = 0:6024
m
X
2;1 = em2 m;1 = 0:3858(1) + 0:6142(1) + 0(0:8090) = 1:0000
m
X
2;2 = em2 m;2 = 0:3858(1) + 0:6142(1) + 0(0:8090) = 1:0000
m
X
2;33 = em2 m;33 = 0:3858(0:4361) + 0:6142(0:4361) + 0(1) = 0:4361
m

k
i 1 2 33
i;k =
1 0.9436 0.9436 0.6024
2 1.0000 1.0000 0.4361

Calculate the sk vector (size equal to number of subgroups) from

X
sk = m m;k
m
X
s1 = m m;1 = 0:4342(1) + 0:4700(1) + 0:0958(0:8090) = 0:9817
m
X
s2 = m m;2 = 0:4342(1) + 0:4700(1) + 0:0958(0:8090) = 0:9817
m
X
s33 = m m;33 = 0:4342(0:4361) + 0:4700(0:4361) + 0:0958(1) = 0:4901
m

One last step before you are ready to calculate the combinatorial and residual parts
of the activity coe¢ cients is to calculate the volume and surface area contributions
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for the molecules i.e.,

ri
Ji = P
xj rj
j
r1 3:6836
J1 = P = = 0:8046
xj rj 0:4(3:6836) + 0:6(5:1742)
j
r2 5:1742
J2 = P = = 1:1302
xj rj 0:4(3:6836) + 0:6(5:1742)
j

qi
Li = P
xj qj
j
q1 3:1720
L1 = P = = 0:812
xj qj 0:4(3:1720) + 0:6(4:3960)
j
q2 4:3960
L2 = P = = 1:1253
xj qj 0:4(3:1720) + 0:6(4:3960)
j

Calculate the combinatorial activity coe¢ cients from

C Ji Ji
ln i =1 Ji + ln Ji 5qi 1 + ln
Li Li
C J1 J1
ln 1 =1 J1 + ln J1 5q1 (1 + ln )
L1 L1
0:8046 0:8046 2
=1 0:8046 + ln(0:8046) 5(3:1720)(1 + ln )= 2: 134 7 10
0:812 0:812
C J2 J2
ln 2 =1 J2 + ln J2 5q2 (1 + ln )
L2 L2
1:1302 1:1302 3
=1 1:1302 + ln 1:1302 5(4:3960)(1 + ln )= 7: 597 6 10
1:1253 1:1253
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Determine the residual part of the activity coe¢ cients from

" #
X i;k i;k
ln Ri = qi 1 k ek;i ln
sk sk
k
" #
X 1;k 1;k
R
ln 1 = q1 1 k ek;1 ln
sk sk
k
0:9436 0:9436
= 3:1720(1 (0:4342 0:5347 ln
0:9817 0:9817
0:9436 0:9436
+0:4700 0:1702 ln
0:9817 0:9817
0:6024 0:6024
+0:0958 0:2951 ln ))
0:4901 0:4901
= 0:14630
" #
X 2;k 2;k
R
ln 2 = q2 1 k ek;2 ln
sk sk
k
1:0000 1:0000
= 4:396(1 (0:4342 0:3858 ln
0:9817 0:9817
1:0000 1:0000
+0:4700 0:6142 ln
0:9817 0:9817
0:4360 0:4360
+0:0958 0:0000 ln ))
0:4901 0:4901
= 5: 358 3 10 2

R C
ln i = ln i + ln i
R C 2
ln 1 = ln 1 + ln 1 = 0:14630 + ( 2: 134 7 10 ) = 0:124 95
1 = exp(0:124 95) = 1: 133
R C 2 3 2
ln 2 = ln 2 + ln 2 = 5: 358 3 10 + ( 7: 597 6 10 ) = 4: 598 5 10
2
2 = exp(4: 598 5 10 ) = 1: 047 :